基于动态亚胺键的生物基自修复可回收聚氨酯的制备及性能
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中国林业科学研究院南京林产化学工业研究所,江苏 南京 210047

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江苏省生物质能源与材料重点实验室项目(JSBEM-S-202006);国家自然科学基金青年基金资助项目(31901256);国家自然科学基金资助项目( 32071712)


Preparation and Properties of Bio-Based Self-Healing and Recyclable Polyurethane Elastomer Based on Dynamic Iimine Bonds
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    摘要:

    研发生物基自修复聚氨酯材料不仅可以满足实际应用需求,也符合绿色可持续发展战略。本文采用糠胺为起始原料,合成了一种生物基呋喃二胺,与香草醛发生曼尼希反应,得到含有动态亚胺键的席夫碱。作为扩链剂与聚氨酯预聚体混合后,最终获得一种兼具自修复和可回收性的聚氨酯弹性体。通过分子设计,调节软硬段比例来控制聚氨酯的机械性能和自修复性能。通过核磁,红外证明了席夫碱的形成,差热扫描量热法(DSC),偏光共振显微镜(POM)和万能拉力试验机系统研究了可逆亚胺键的引入对弹性体自修复和可回收性能的影响。当硬段,软段,扩链剂摩尔比为3:1:2时,弹性体80的下加热2h,自修复效率可达97.5%。同时,动态亚胺键的存在使得材料在室温条件下即可实现再次回收。所有的结果表明,上述聚氨酯弹性体具有优异的自修复及可回收性能,生物基席夫碱在在绿色复合材料的修复再利用方面有巨大的应用潜力。

    Abstract:

    The preparation of self-healing polyurethane materials from renewable resources can not only meet the needs of practical applications, but also matches the green sustainable development strategies.Bio-based furandiamine was synthesized from furfurylamine, and further reacted with vanillin through Mannich reaction to obtain Schiff base containing dynamic imine bonds. The synthesized Schiff base was empolyed as a chain extender and mixed with polyurethane prepolymers, a polyurethane with self-healing and recyclability was prepared. The mechanical properties and self-healing properties of polyurethane can be controlled by simply adjusting the ratio of soft and hard segments. The formation of Schiff bases was demonstrated by NMR and IR. Then, the self-healing and recyclable properties of elastomers was systematically investigated by Differential scanning calorimetry (DSC), polarized light resonance microscopy (POM), and tensile testing. When the molar ratio of hard segment, soft segment and chain extender is 3:1:2, and the elastomer was heated at 80°C for 2 hours, the self-healing efficiency can reach 97.5%. At the same time, the existence of dynamic imine bonds enables the material to be recycled again at room temperature. All the results show that the above-mentioned polyurethane elastomers have excellent self-healing efficiency and recyclable properties, providing potential applications as promising bio-based schiff bases in repairing the cracks quickly generated in composites that require recyclability as well as sustainability.

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  • 收稿日期:2022-04-19
  • 最后修改日期:2022-06-29
  • 录用日期:2022-07-20
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